In Situ Water Quality Monitoring Using an Optical Multiparameter Sensor Probe.

Optical methods such as ultraviolet/visible (UV/Vis) and fluorescence spectroscopy are well-established analytical techniques for in situ water quality monitoring. A broad range of bio-logical and chemical contaminants in different concentration ranges can be detected using these methods. The availability of results in real time allows a quick response to water quality changes. The measuring devices are configured as portable multi-parameter probes. However, their specification and data processing typically cannot be changed by users, or only with difficulties. Therefore, we developed a submersible sensor probe, which combines UV/Vis and fluorescence spectroscopy together with a flexible data processing platform. Due to its modular design in the hardware and software, the sensing system can be modified to the specific application. The dimension of the waterproof enclosure with a diameter of 100 mm permits also its application in groundwater monitoring wells. As a light source for fluorescence spectroscopy, we constructed an LED array that can be equipped with four different LEDs. A miniaturized deuterium-tungsten light source (200-1100 nm) was used for UV/Vis spectroscopy. A miniaturized spectrometer with a spectral range between 225 and 1000 nm permits the detection of complete spectra for both methods.

Membrane inlet-ion mobility spectrometry with automatic spectra evaluation as online monitoring tool for the process control of microalgae cultivation.

The cultivation of algae either in open raceway ponds or in closed bioreactors could allow the renewable production of biomass for food, pharmaceutical, cosmetic, or chemical industries. Optimal cultivation conditions are however required to ensure that the production of these compounds is both efficient and economical. Therefore, high-frequency analytical measurements are required to allow timely process control and to detect possible disturbances during algae growth. Such analytical methods are only available to a limited extent. Therefore, we introduced a method for monitoring algae release volatile organic compounds (VOCs) in the headspace above a bioreactor in real time. This method is based on ion mobility spectrometry (IMS) in combination with a membrane inlet (MI). The unique feature of IMS is that complete spectra are detected in real time instead of sum signals. These spectral patterns produced in the ion mobility spectrum were evaluated automatically via principal component analysis (PCA). The detected peak patterns are characteristic for the respective algae culture; allow the assignment of the individual growth phases and reflect the influence of experimental parameters. These results allow for the first time a continuous monitoring of the algae cultivation and thus an early detection of possible disturbances in the biotechnological process.

Drift Time Corrections Based on a Practical Measurement of the Depletion Zone to Allow Accurate and Reproducible Determination of the Reduced Mobility of Ions in DT-IMS.

The reduced mobility of an ion is a key parameter for identifying ions and comparing spectra in drift time ion mobility spectrometry. As the resolution of spectrometers improves, accurate determination of the reduced mobility is increasingly important. The drift time, used to calculate the reduced mobility, is affected by the ion gate, and this effect has previously been compensated with a linear correction. These corrections, however, do not allow for changes in the distances that the ions must drift to reach the detector caused by the electric field around the ion gate. As these corrections are a linear correction, nonlinearity in the influence of the ion gate may also lead to greater errors. By measuring the length of the depletion zone in front of the ion gate the extra distance traveled by the ions may be corrected for. This measurement also provides the boundary conditions for when a correction to the drift time may be accurately applied. This work shows that the length of the depletion zone can be experimentally measured and that it is consistent for a particular geometry of ion gate.

Molecularly Imprinted Polymer-Based Sensors for Priority Pollutants.

Globally, there is growing concern about the health risks of water and air pollution. The U.S. Environmental Protection Agency (EPA) has developed a list of priority pollutants containing 129 different chemical compounds. All of these chemicals are of significant interest due to their serious health and safety issues. Permanent exposure to some concentrations of these chemicals can cause severe and irrecoverable health effects, which can be easily prevented by their early identification. Molecularly imprinted polymers (MIPs) offer great potential for selective adsorption of chemicals from water and air samples. These selective artificial bio(mimetic) receptors are promising candidates for modification of sensors, especially disposable sensors, due to their low-cost, long-term stability, ease of engineering, simplicity of production and their applicability for a wide range of targets. Herein, innovative strategies used to develop MIP-based sensors for EPA priority pollutants will be reviewed.

Rational Design of Molecularly Imprinted Polymers Using Quaternary Ammonium Cations for Glyphosate Detection.

Molecularly imprinted polymers have emerged as cost-effective and rugged artificial selective sorbents for combination with different sensors. In this study, quaternary ammonium cations, as functional monomers, were systematically evaluated to design imprinted polymers for glyphosate as an important model compound for electrically charged and highly water-soluble chemical compounds. To this aim, a small pool of monomers were used including (3-acrylamidopropyl)trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium chloride, and diallyldimethylammonium chloride. The simultaneous interactions between three positively charged monomers and glyphosate were preliminary evaluated using statistical design of the experiment method. Afterwards, different polymers were synthesized at the gold surface of the quartz crystal microbalance sensor using optimized and not optimized glyphosate-monomers ratios. All synthesized polymers were characterized using atomic force microscopy, contact angle, Fourier-transform infrared, and X-ray photoelectron spectroscopy. Evaluated functional monomers showed promise as highly efficient functional monomers, when they are used together and at the optimized ratio, as predicted by the statistical method. Obtained results from the modified sensors were used to develop a simple model describing the binding characteristics at the surface of the different synthesized polymers. This model helps to develop new synthesis strategies for rational design of the highly selective imprinted polymers and to use as a sensing platform for water soluble and polar targets.

Application of Low-Cost Electrochemical Sensors to Aqueous Systems to Allow Automated Determination of NH3 and H2S in Water.

Usage of commercially available electrochemical gas sensors is currently limited by both the working range of the sensor with respect to temperature and humidity and the spikes in sensor response caused by sudden changes in temperature or humidity. Using a thermostatically controlled chamber, the sensor response of ammonia and hydrogen sulfide sensors was studied under extreme, rapidly changing levels of humidity with the aim of analyzing nebulized water samples. To protect the sensors from damage, the gas stream was alternated between a saturated gas stream from a Flow Blurring® nebulizer and a dry air stream. When switching between high and low humidity gas streams, the expected current spike was observed and mathematically described. Using this mathematical model, the signal response due to the change in humidity could be subtracted from the measured signal and the sensor response to the target molecule recorded. As the sensor response is determined by the model while the sensor is acclimatizing to the new humid conditions, a result is calculated faster than that by systems that rely on stable humidity. The use of the proposed mathematical model thus widens the scope of electrochemical gas sensors to include saturated gas streams, for example, from nebulized water samples, and gas streams with variable humidity.

Humidity Effect on the Drift Times of the Reactant Ions in Ion Mobility Spectrometry.

The effect of moisture content on the drift times of NH4+ and H3O+ reactant ions at different temperatures was experimentally and theoretically studied using an ion mobility spectrometer (IMS). The peak positions of the ions shifted to higher drift times as the humidity of the drift gas increased. The peak displacements were attributed to the consecutive formation of hydrated ion clusters, RI+(H2O)n. Using chemical equilibrium relations and thermodynamic data derived from DFT calculation, a model was proposed to formulate the change in the drift times as 1/td = 1/tdΘ - ßT log[H2O], where ß is a constant and T is temperature. [H2O] is the concentration of water in ppm and, tdΘ is the drift time at the standard condition of [H2O] = 1 ppm. The proposed equation perfectly predicted the change in the drift times of the reactant ions as a function of the moisture in the drift gas. Accordingly, standard mobility, K = KΘ - γT ln[H2O], was defined, which is independent of the moisture level of the drift gas and reflects the chemical reactivity. In this work, it is proposed to correct the reported reduced mobilities for the moisture to a standard condition of 1 ppm water concentration, in a similar manner to the corrections to the standard temperature and pressure of 273 K and 760 mbar, respectively. Finally, the likelihood that different hydrates forms of the reactant ion exist is discussed based on the entropy concept.

Molecularly Imprinted Polymer Materials as Selective Recognition Sorbents for Explosives: A Review.

Explosives are of significant interest to homeland security departments and forensic investigations. Fast, sensitive and selective detection of these chemicals is of great concern for security purposes as well as for triage and decontamination in contaminated areas. To this end, selective sorbents with fast binding kinetics and high binding capacity, either in combination with a sensor transducer or a sampling/sample-preparation method, are required. Molecularly imprinted polymers (MIPs) show promise as cost-effective and rugged artificial selective sorbents, which have a wide variety of applications. This manuscript reviews the innovative strategies developed in 57 manuscripts (published from 2006 to 2019) to use MIP materials for explosives. To the best of our knowledge, there are currently no commercially available MIP-modified sensors or sample preparation methods for explosives in the market. We believe that this review provides information to give insight into the future prospects and potential commercialization of such materials. We warn the readers of the hazards of working with explosives.

Negative electrospray ionization ion mobility spectrometry combined with paper-based molecular imprinted polymer disks: A novel approach for rapid target screening of trace organic compounds in water samples.

A novel approach for the rapid target screening of water contaminants in trace concentrations was applied for the determination of the artificial sweetener Acesulfame-K, an accepted municipal wastewater indicator. This new method combines the selective enrichment of target analytes on paper-based molecular imprinted polymer disks and the subsequent analysis using a modified ion mobility spectrometer allowing negative electrospray ionization (ESI-IMS). Our developed ion mobility spectrometer permits the sensitive detection of Acesulfame with a limit of detection of 93 µg L-1 within few seconds without sample separation. The use of modified paper filters for fast extraction and enrichment of the target substance from water samples results in a lower limit of detection of 0.19 µg L-1. This procedure is directly applicable in the field, the transport and the proper storage of bulky sample bottles is avoided. The capability of the procedure developed was demonstrated by measuring real samples from a river at locations upstream and downstream of the effluent of the central municipal waste water treatment plant. The quantitative data of ion mobility measurements show a very good agreement with those obtained with the commonly used standard procedure (high performance liquid chromatography-tandem mass spectrometry).

A new strategy for accelerated extraction of target compounds using molecularly imprinted polymer particles embedded in a paper-based disk.

In this study, a general simple and inexpensive method is introduced for the preparation of a paper-based selective disk-type solid phase extraction (SPE) technique, appropriate for fast and high throughput monitoring of target compounds. An ion exchange molecularly imprinted polymer (MIP) was synthesized for the extraction and analysis of acesulfame, an anthropogenic water quality marker. Acesulfame imprinting was used as an example for demonstrating the benefits of a nanosized, swellable MIP extraction sorbents integrated in an on-site compatible concept for water quality monitoring. Compared with an 8 mL standard SPE cartridge, the paper-based MIP disk (47 mm ø) format allowed (1) high sample flow rates up to 30 mL•min-1 without losing extraction efficiency (2) extracting sample volumes up to 500 mL in much shorter times than with standard SPE, (3) the reuse of the disks (up to 3 times more than SPE cartridge) due to high robustness and an efficient post-cleaning, and (4) reducing the sampling time from 100 minutes (using the standard SPE format) to about 2 minutes with the MIP paper disk for 50 mL water sample. Different parameters like cellulose fiber/polymer ratios, sample volume, sample flow-rate, washing, and elution conditions were evaluated and optimized. Using developed extraction technique with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis, a new protocol was established that provides detection and quantification limits of 0.015 µg•L-1 and 0.05 µg•L-1 , respectively. The developed paper disks were used in-field for the selective extraction of target compounds and transferred to the laboratory for further analysis.

Ion transfer from an atmospheric pressure ion funnel into a mass spectrometer with different interface options: Simulation-based optimization of ion transmission efficiency.

RATIONALE: We optimized an atmospheric pressure ion funnel (APIF) including different interface options (pinhole, capillary, and nozzle) regarding a maximal ion transmission. Previous computer simulations consider the ion funnel itself and do not include the geometry of the following components which can considerably influence the ion transmission into the vacuum stage. METHODS: Initially, a three-dimensional computer-aided design (CAD) model of our setup was created using Autodesk Inventor. This model was imported to the Autodesk Simulation CFD program where the computational fluid dynamics (CFD) were calculated. The flow field was transferred to SIMION 8.1. Investigations of ion trajectories were carried out using the SDS (statistical diffusion simulation) tool of SIMION, which allowed us to evaluate the flow regime, pressure, and temperature values that we obtained. RESULTS: The simulation-based optimization of different interfaces between an atmospheric pressure ion funnel and the first vacuum stage of a mass spectrometer require the consideration of fluid dynamics. The use of a Venturi nozzle ensures the highest level of transmission efficiency in comparison to capillaries or pinholes. However, the application of radiofrequency (RF) voltage and an appropriate direct current (DC) field leads to process optimization and maximum ion transfer. The nozzle does not hinder the transfer of small ions. CONCLUSIONS: Our high-resolution SIMION model (0.01 mm grid unit(-1) ) under consideration of fluid dynamics is generally suitable for predicting the ion transmission through an atmospheric-vacuum system for mass spectrometry and enables the optimization of operational parameters. A Venturi nozzle inserted between the ion funnel and the mass spectrometer permits maximal ion transmission. Copyright © 2015 John Wiley & Sons, Ltd.

Ion-exchange molecularly imprinted polymer for the extraction of negatively charged acesulfame from wastewater samples.

Acesulfame is a known indicator that is used to identify the introduction of domestic wastewater into water systems. It is negatively charged and highly water-soluble at environmental pH values. In this study, a molecularly imprinted polymer (MIP) was synthesized for negatively charged acesulfame and successfully applied for the selective solid phase extraction (SPE) of acesulfame from influent and effluent wastewater samples. (Vinylbenzyl)trimethylammonium chloride (VBTA) was used as a novel phase transfer reagent, which enhanced the solubility of negatively charged acesulfame in the organic solvent (porogen) and served as a functional monomer in MIP synthesis. Different molecularly imprinted polymers were synthesized to optimize the extraction capability of acesulfame. The different materials were evaluated using equilibrium rebinding experiments, selectivity experiments and scanning electron microscopy (SEM). The most efficient MIP was used in a molecularly imprinted-solid phase extraction (MISPE) protocol to extract acesulfame from wastewater samples. Using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis, detection and quantification limits were achieved at 0.12µgL(-1) and 0.35µgL(-1), respectively. Certain cross selectivity for the chemical compounds containing negatively charged sulfonamide functional group was observed during selectivity experiments.

Selective mixed-bed solid phase extraction of atrazine herbicide from environmental water samples using molecularly imprinted polymer.

A novel approach for the selective extraction of organic target compounds from water samples has been developed using a mixed-bed solid phase extraction (mixed-bed SPE) technique. The molecularly imprinted polymer (MIP) particles are embedded in a network of silica gel to form a stable uniform porous bed. The capabilities of this method are demonstrated using atrazine as a model compound. In comparison to conventional molecularly imprinted-solid phase extraction (MISPE), the proposed mixed-bed MISPE method in combination with gas chromatography-mass spectrometry (GC-MS) analysis enables more reproducible and efficient extraction performance. After optimization of operational parameters (polymerization conditions, bed matrix ingredients, polymer to silica gel ratio, pH of the sample solution, breakthrough volume plus washing and elution conditions), improved LODs (1.34 µg L(-1) in comparison to 2.25 µg L(-1) obtained using MISPE) and limits of quantification (4.5 µg L(-1) for mixed-bed MISPE and 7.5 µg L(-1) for MISPE) were observed for the analysis of atrazine. Furthermore, the relative standard deviations (RSDs) for atrazine at concentrations between 5 and 200 µg L(-1) ranged between 1.8% and 6.3% compared to MISPE (3.5-12.1%). Additionally, the column-to-column reproducibility for the mixed-bed MISPE was significantly improved to 16.1%, compared with 53% that was observed for MISPE. Due to the reduced bed-mass sorbent and at optimized conditions, the total amount of organic solvents required for conditioning, washing and elution steps reduced from more than 25 mL for conventional MISPE to less than 2 mL for mixed-bed MISPE. Besides reduced organic solvent consumption, total sample preparation time of the mixed-bed MISPE method relative to the conventional MISPE was reduced from more than 20 min to less than 10 min. The amount of organic solvent required for complete elution diminished from 3 mL (conventional MISPE) to less than 0.4 mL with the mixed-bed technique shows its inherent potential for online operation with an analytical instrument. In order to evaluate the selectivity and matrix effects of the developed mixed-bed MISPE method, it was applied as an extraction technique for atrazine from environmental wastewater and river water samples.

Accuracy of ion mobility measurements dependent on the influence of humidity.

Measurements with sensor techniques in field analytical chemistry can be considerably affected by varying ambient conditions such as humidity. We systematically investigated the way in which ion mobility measurements are influenced by moisture. Both the peak positions of product ions within the spectrum and their relative abundance can vary depending on humidity. The transportation of humidity via the carrier gas into the ion mobility spectrometer causes changes in ionization pathways. Additional reactant ion species are formed and a lower relative abundance of product ions from halogenated compounds was generally observed. The peak position within the ion mobility spectrum is comparatively unaffected for the same ions. In contrast, considerable differences in drift times detected were found with increasing humidity of drift gas, while the influence on calibration was not as significant for chlorinated and brominated substances as observed for humid carrier gases.

A new strategy for synthesis of an in-tube molecularly imprinted polymer-solid phase microextraction device: selective off-line extraction of 4-nitrophenol as an example of priority pollutants from environmental water samples.

In this study a novel preparation protocol has been developed for the construction of an in-tube molecularly imprinted polymer-solid phase microextraction (MIP-SPME) device. Open tubular capillaries have been molded from a polymer sorbent imprinted for 4-nitrophenol as target molecule. Different parameters like inner diameter and volume of the polymer, porogen volume, swelling and shrinking effects of the polymer tubes, polymerization time, pH of the sample, extraction time, 'salting out' effect and serial connection of the tubes were evaluated and optimized. Particularly, an optimized polymer preparation process and extraction condition enhanced the final extraction recovery of 4-nitrophenol substantially. Using this new MIP-SPME technique with high-performance liquid chromatography-ultraviolet (HPLC-UV) analysis of the extracts, the linear range and the limits of detection and quantification are 0.001-10 mg L(-1), 0.33 µg L(-1) and 1.1 µg L(-1) respectively. At optimized conditions, a mixture of nitrophenols, alkylated and chlorinated phenols spiked into municipal waste water were analyzed to evaluate the matrix effects and cross selectivity of the new MIP capillary tubes.

A solid-phase microextraction method for the in vivo sampling of MTBE in common reed (Phragmites australis).

Phytoscreening of phytoremediation-based plantings is discussed as a promising monitoring tool in literature. We developed and applied an analytical procedure for the in vivo sampling of methyl tert-butyl ether (MTBE) in the common reed (Phragmites australis) from a phytoremediation site highly polluted with MTBE. The approach uses solid-phase microextraction (SPME) with the SPME fibre directly introduced into the aerenchyma of the plant stem. For optimising the analytical procedure and estimating the capability of the proposed method, laboratory tests on the microcosm scale and field studies over one vegetation period were carried out. Furthermore, the results of in vivo SPME sampling were compared with those obtained with the traditional approach for analysing plants using dynamic headspace analysis. The MTBE signals detected within the plants were also correlated with the concentration in the water phase. The discussion of results showed the feasibility of the proposed method for a qualitative phytoscreening of volatile organic compounds present in wetland plants.

Temperature dependence of ion mobility signals of halogenated compounds.

Ion mobility spectrometry (IMS) as handheld and transportable sensor technique permits the sensitive detection of halogenated compounds with importance in environmental monitoring and process control. The negative ion mobility spectra mostly show one product ion peak which can be attributed to (H(2)O)(n)X(-) ions due to dissociative electron attachments. For minimizing memory effects and contaminations, modern ion mobility spectrometers work at elevated temperatures. In this paper, we investigated the influence of temperature on peak position, resolution and relative abundance of ions formed from halogenated substances. Elevated temperatures affect the peak position in different way. For fluorine- and chlorine-containing product ions, changes in hydration and clustering have a considerable influence on peak position, while these processes are of minor importance for bromine- and iodine-containing product ions. In these cases, the drift time differences mainly result from differences in drift behavior due to differences in gas density, the mean free path of ions and different collision rates. The drift time shift with elevated temperatures provides an enhanced peak-to-peak resolution. Improved separation efficiency can therefore be established with increased temperatures for negative product ions of halogenated compounds. Furthermore, an enhanced sensitivity was found for all compounds with increasing temperatures. However, independent on the temperature, the order of sensitivity is mainly determined by the bonding state of halogen atoms within the molecules.

Comparative evaluation of pilot scale horizontal subsurface-flow constructed wetlands and plant root mats for treating groundwater contaminated with benzene and MTBE.

In order to evaluate technology options for the treatment of groundwater contaminated with benzene and MTBE in constructed wetlands (CWs), a scarcely applied plant root mat system and two horizontal subsurface-flow (HSSF) CWs were investigated. The inflow load of benzene and MTBE were 188-522 and 31-90 mg d(-1)m(-2), respectively. Higher removal efficiencies were obtained during summer in all systems. The benzene removal efficiencies were 0-33%, 24-100% and 22-100% in the unplanted HSSF-CW, planted HSSF-CW and the plant root mat, respectively; the MTBE removal efficiencies amounted to 0-33%, 16-93% and 8-93% in the unplanted HSSF-CW, planted HSSF-CW and the plant root mat, respectively. The volatilisation rates in the plant root mat amounted to 7.24 and 2.32 mg d(-1)m(-2) for benzene and MTBE, which is equivalent to 3.0% and 15.2% of the total removal. The volatilisation rates in the HSSF-CW reached 2.59 and 1.07 mg d(-1)m(-2), corresponding to 1.1% and 6.1% of the total removal of benzene and MTBE, respectively. The results indicate that plant root mats are an interesting option for the treatment of waters polluted with benzene and MTBE under moderate temperatures conditions.

Performance evaluation using a three compartment mass balance for the removal of volatile organic compounds in pilot scale constructed wetlands.

To perform a general assessment of treatment efficiency, a mass balance study was undertaken for two types of constructed wetlands (CWs), planted gravel filters and plant root mat systems, for treating VOC (benzene; MTBE) polluted groundwater under field conditions. Contaminant fate was investigated in the respective water, plant, and atmosphere compartments by determining water and atmospheric contaminant loads and calculating contaminant plant uptake, thereby allowing for an extended efficiency assessment of CWs. Highest total VOC removal was achieved during summer, being pronounced for benzene compared to MTBE. According to the experimental results and the calculations generated by the balancing model, degradation in the rhizosphere and plant uptake accounted for the main benzene removal processes, of 76% and 13% for the gravel bed CW and 83% and 11% for the root mat system. Volatilization flux of benzene and MTBE was low (<5%) for the gravel bed CW, while in the root mat system direct contact of aqueous and gaseous phases favored total MTBE volatilization (24%). With this applied approach, we present detailed contaminant mass balances that allow for conclusive quantitative estimation of contaminant elimination and distribution processes (e.g., total, surface, and phytovolatilization, plant uptake, rhizodegradation) in CWs under field conditions.

Response of halogenated compounds in ion mobility spectrometry depending on their structural features.

Ion mobility spectrometry (IMS) with handheld and transportable devices permits the sensitive detection of chlorinated compounds which are important in environmental monitoring. The ion mobility spectra in negative measuring modus mostly show one product ion peak [(H(2)O)(n)Cl(-)] due to dissociative electron attachments. In this paper, we investigated relevant chlorinated compounds (R-Cl) where R represents allyl-, benzyl-, phenyl-, alkyl- and vinyl-groups. These groups cause differences in the R-Cl bond strength and differences in the cleavage of chlorine can therefore be expected. All chlorinated substances investigated provide the same product ion peak at 2.75 cm(2)Vs(-1) independent on the different C-Cl bond strength. However, distinct influences of structural features on the peak intensities of the (H(2)O)(n)Cl(-) product ion peak were established. Generally, increasing sensitivities were obtained in the order chlorobenzenes